EP2366038A1 - Method for recovering metals contained in electronic waste - Google Patents

Method for recovering metals contained in electronic waste

Info

Publication number
EP2366038A1
EP2366038A1 EP09771778A EP09771778A EP2366038A1 EP 2366038 A1 EP2366038 A1 EP 2366038A1 EP 09771778 A EP09771778 A EP 09771778A EP 09771778 A EP09771778 A EP 09771778A EP 2366038 A1 EP2366038 A1 EP 2366038A1
Authority
EP
European Patent Office
Prior art keywords
magnetic
residues
pyrolysis
materials
ferrous metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09771778A
Other languages
German (de)
French (fr)
Other versions
EP2366038B1 (en
Inventor
Christian Thomas
Joël MENUET
Gervais Vanhelle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Igneo France SAS
Original Assignee
Terra Nova SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Terra Nova SAS filed Critical Terra Nova SAS
Priority to SI200931839T priority Critical patent/SI2366038T1/en
Priority to PL09771778T priority patent/PL2366038T3/en
Publication of EP2366038A1 publication Critical patent/EP2366038A1/en
Application granted granted Critical
Publication of EP2366038B1 publication Critical patent/EP2366038B1/en
Priority to HRP20180734TT priority patent/HRP20180734T1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
    • B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
    • B07C5/34—Sorting according to other particular properties
    • B07C5/344—Sorting according to other particular properties according to electric or electromagnetic properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for recovering metals contained in electronic waste, in particular used electronic cards, and an installation adapted to the implementation of this method.
  • One known metal recovery technique is to load the waste (previously ground about 4 cm) into primary furnaces or copper furnaces. This technique generates high emissions of dust, sulfur dioxide and gases containing halogens (chlorine and bromine). The gases emitted therefore require complex subsequent processing.
  • Another problem with this technique is that electronic waste gives off a lot of heat during the combustion of the plastic they contain. In other words, the high calorific value of electronic waste is an obstacle to this technique.
  • the aluminum content often high in treated waste is another problem, since the presence of aluminum in the slag or dairy increases their melting temperature so that their treatment becomes very difficult. Because of these various disadvantages, the capacity of primary furnaces for processing electronic waste is limited.
  • the document EP 1712301 describes a method of processing electronic waste in which the metal wire fragments are recovered from the waste by means of a barrel provided with a textile band to which the wire fragments adhere.
  • the invention firstly relates to a method for treating materials containing a mixture of plastics and metal materials, said method comprising:
  • a first magnetic separation carried out on the pyrolyzed materials, providing on the one hand a ferrous metal fraction and on the other hand non-ferrous residues;
  • the materials are electronic waste, preferably used electronic cards.
  • the grinding is performed up to a sieve pass Dmax less than or equal to 50 mm, preferably between 20 and 30 mm.
  • the pyrolysis is carried out at a temperature of between 300 and 600 ° C. and / or with an air factor of between 0.7 and 0.98.
  • the first magnetic separation is performed by means of a magnet or electromagnet.
  • the second magnetic separation is performed by means of an eddy current separator.
  • the method also comprises a step of combustion of the gases resulting from the pyrolysis, possibly followed by a step of neutralization of the gases with sodium bicarbonate.
  • the ferrous metal fraction comprises iron and / or iron derivatives, and possibly gold.
  • the non-ferrous metal fraction comprises aluminum and / or zinc.
  • the non-magnetic residues comprise copper, lead, tin, glass fibers, carbon and / or precious metals, in particular gold, silver, platinum , palladium, rhodium, ruthenium, iridium and / or osmium.
  • the ferrous metal fraction is combined with the non-magnetic residues after the second magnetic separation.
  • the method comprises a subsequent step of treatment of the non-magnetic residues making it possible to recover the copper contained in the non-magnetic residues and / or to recover precious metals contained in the non-magnetic residues, in particular chosen among gold, silver, lead, tin, platinum, palladium, rhodium, ruthenium, iridium and / or osmium.
  • the invention also relates to a material treatment plant containing a mixture of plastics and metallics, comprising successively online:
  • the grinding means are adapted to carry out grinding up to a sieve pass Dmax less than or equal to 50 mm, preferably between 20 and 30 mm.
  • the primary magnetic separator comprises a magnet or electromagnet disposed above a conveyor belt.
  • the secondary magnetic separator comprises an eddy current separator.
  • the installation also comprises a pyrolysis gas collection pipe supplying a combustion chamber, and optionally, at the outlet of the combustion chamber, a contact chamber fed by a supply of activated carbon and a supply of of baking soda.
  • the present invention overcomes the disadvantages of the state of the art. In particular, it provides a simple and energy-efficient process for obtaining a good yield of recycled metals.
  • the invention also has one or more of the advantageous features listed below.
  • the process according to the invention makes it possible to eliminate the epoxy resins and the plastics constituents of the electronic boards as well as chlorine and a large part of the bromine while avoiding a loss of metals by oxidation or distillation, taking into account the low temperature and the conditions non-oxidizing operation.
  • the material is thus concentrated in metals.
  • the method according to the invention makes it possible, during the cooling of the combustion gases, produced during pyrolysis, to recover the energy contained in these gases under good conditions.
  • the material thus pyrolyzed can be treated advantageously in the conventional tools of copper metallurgy by overcoming certain technological limitations of these tools and more precisely the content of volatile matter (carbon chains) and halogens.
  • the decomposition of the epoxy resins during pyrolysis has the effect of liberating all the integral components of the support: copper, electronic components, metal components ...
  • This separation of the support allows a very efficient use of mag- netic sorting (more effective than the separation that would be achieved by very fine grinding).
  • the process according to the invention makes it possible to maximize the recovery efficiency of the metals, that is to say to minimize the losses of metals during the process.
  • the process according to the invention makes it possible to separate the aluminum from the other metals during the process, so as to facilitate the downstream processing of the metals recovered.
  • aluminum indeed has a behavior that is detrimental to the fluidity of the slag.
  • aluminum because of its chemical reactivity leads to overconsumption of chemical reagents.
  • the treatment of pyrolysis gases makes the process clean without requiring heavy handling of halogens, sulfur compounds or heavy metal emissions.
  • FIG. 1 schematically represents an example of an electronic waste treatment installation according to the invention.
  • an electronic waste processing facility schematically comprises the following elements.
  • the grinding and sampling means may include a main crusher to reduce the size of waste to less than 50 mm, a primary sampler to collect a primary sample representative of the total flow (for example 10% of the total flow), a second crusher for grinding the primary sample at a size of 10 mm, a secondary sampler representative of the primary sample (for example 10% of the flow of the primary sample), possibly a third mill and a tertiary sampler.
  • a preferred example of a main mill is a knife mill equipped with a 25 mm grid. This type of mill has the advantage of limiting the production of fines.
  • a crushed waste feed line 3 feeds a pyrolysis plant 4 with crushed waste.
  • a buffer silo (not shown) can be provided between the grinding and sampling means. 2 and the pyrolysis plant 4.
  • the pyrolysis plant 4 can in particular, be of the type of oven, reverberatory oven, rotary kiln, fluidized bed furnace, multi-storey oven ...
  • the pyrolysis plant 4 is a multi-stage furnace, for example approximately 100 m 2 , heated directly with gas.
  • the power of the installation can typically be about 1000 kW.
  • a pyrolytic residue feed line 5 At the outlet of the pyrolysis plant 4 there is provided a pyrolytic residue feed line 5 and a pyrolysis gas collection pipe 15.
  • the pyrolyzed residue feed line 5 feeds cooling means 6.
  • the cooling means 6 may in particular comprise a heat exchanger.
  • a jacketed screw of approximately 50 m 2 surface and cooled with water may in particular be appropriate.
  • a cooled residue feeding line 7 feeds a primary magnetic separator 8.
  • the primary magnetic separator 8 can be a simple electromagnet disposed above a conveyor belt.
  • a ferrous metal fraction recovery line 9 and a non-ferrous residue recovery line 10 are connected at the output of the primary magnetic separator 8.
  • the non-ferrous waste recovery line 10 in turn feeds a secondary magnetic separator 11, a device specially designed for this function.
  • the secondary magnetic separator 11 may for example use eddy currents.
  • a non-ferrous metal fraction recovery line 12 and a non-magnetic residue recovery line 13 are connected at the output of the secondary magnetic separator 11.
  • the non-magnetic residue recovery line 13 supplies conditioning means 14 in turn.
  • the pyrolysis gas collection pipe 15 feeds a combustion chamber 17, which is also fed by an air inlet pipe 16.
  • the combustion chamber 17 may be of the metallic cylindrical chamber type protected by one or more layers of bricks.
  • the cooling means 19 may for example consist of a cooling tower 19 supplied with a water spray injection. , or a heat exchanger for flue gas (air-fumes or water-fumes).
  • a collection duct for the cooled combustion products 26 is connected at the outlet of the cooling means 19 and supplies a contact chamber 29.
  • a supply of activated carbon 27 and a supply of sodium bicarbonate 28 are also provided at the inlet of the contact chamber 29.
  • the contact chamber 29 may be of the cylindrical type having a sufficient volume to have a residence time of the combustion products of about two seconds.
  • a product collection line 30 feeds a filter 31 at the output of which are provided a purified gas recovery line 33 and a halogen recovery line 32.
  • the filter 31 may be type bag filter or electro-filter.
  • This preliminary cooling system comprises a sampling pipe 21 at the outlet of the combustion chamber 17, which feeds a heat exchanger 24 and then rejoins the collection pipe of the combustion products 18.
  • the heat exchanger 24 is also supplied by a supply of coolant 23.
  • the outlet 25 of the coolant ensures the recovery of energy.
  • Electronic waste used materials comprising electronic components.
  • Electronic waste may include individual electronic components, mobile phones and any other small device containing electronic cards.
  • the electronic scrap comprises or consists of electronic boards, that is to say platelets consisting of printed circuits on which are welded electronic components. The following process is described in connection with the recycling of electronic cards.
  • the method is also applicable in the case of other types of starting materials, namely generally materials (preferably used materials or waste) comprising a metal fraction (including a metal fraction containing precious metals) and a plastic fraction.
  • the plastic fraction can comprise in particular epoxy resins, polyethylene or polyvinyl chloride.
  • the metal fraction can include ferrous metals, copper, lead, aluminum, zinc, precious metals (gold, silver, platinum, palladium, rhodium, ruthenium, iridium, osmium).
  • the process can be applied to automotive grinding residues.
  • the method described here comprises the following 5 main steps:
  • This example corresponds to the use of the processing installation described above in connection with FIG.
  • the treatment capacity is of the order of 3 tons per hour.
  • step (1) the electronic cards are crushed at the level of the grinding means 2.
  • the grinding is preferably carried out to a size Dmax of 25 mm (Dmax being defined as the sieve pass).
  • Dmax being defined as the sieve pass.
  • the crushed cards are then stored in a buffer silo.
  • the buffer silo supplies the pyrolysis plant 4 at about 3 tons per hour, in which pyrolysis of step (2) is carried out.
  • step (2) the ground boards are heated in the oven to a temperature of between 300 and 450 ° C., preferably about 400 ° C., in a suitable reactor, essentially in the absence of oxygen (in reducing or neutral medium). More precisely, the burners are regulated with a defect of air and the air factor (ratio between the combustion air and the theoretical neutral combustion air) is between 0.7 and 0.9.
  • the duration of the pyrolysis is adjusted in order to obtain a complete decomposition of the carbon chains composing the plastic fraction (in particular the chains of the epoxy resins). For example, the duration can be between 10 and 30 minutes.
  • a steam addition of about 1 ton / hour at the levels of the furnace can control the temperature thereof.
  • step (3) the pyrolysis residues pass through the cooling means 6. This step makes it possible to reduce the temperature of the pyrolyzed residues to a temperature of between 60 and 100 ° C.
  • step (4) comprises the actual separation of the metals. This step makes it possible to enrich the solid residue with precious metals and to reduce the concentration of harmful elements in the subsequent treatment of the pyrolysis residue (in particular aluminum).
  • the ferrous metal fraction is extracted from the residues.
  • This ferrous metal fraction mainly comprises iron and iron derivatives, but possibly, depending on the origin of the electronic cards, the ferrous metal fraction may also include (be mixed with) gold. This is particularly the case when the electronic cards are flashed with gold.
  • the ferrous metal moiety does not comprise more than 1% aluminum.
  • the residues freed from the ferrous metal fraction undergo magnetic extraction of the non-ferrous metals at the secondary magnetic separator 11, typically using eddy currents.
  • a non-ferrous metal fraction is extracted, which notably comprises aluminum and zinc.
  • the recovered aluminum can be sold for recycling.
  • the rest of the residues (non-magnetic residues) are recovered via the non-magnetic residue recovery line 13.
  • the non-magnetic residues do not comprise more than 2% of aluminum.
  • the process is carried out so that the metals composing the non-ferrous metal fraction, and primarily aluminum, are not oxidized before the non-ferrous magnetic extraction step.
  • the adjustment of the flame is carried out with a deficit of oxygen (for example 90% of the stoichiometry); in case of indirect heating, the atmosphere must be reducing.
  • the valorization of the ferrous metal fraction may include a recovery of the precious metals it contains for example according to the following processes: recycling of the magnetic part rich in precious metals at the entrance of copper furnaces, and treatment of anode sludges from electro-refining copper anodes poured out of the oven; lead wash of the magnetic part to solubilize precious metals in lead, and treatment of lead according to any conventional method for recovering these precious metals (such as zinc coating, distillation and cupellation, or treatment on a Betts type of electrorefining).
  • Non-magnetic residues include carbon, glass fibers, copper, lead, tin and generally precious metals.
  • the precious metals in question may include gold, silver, platinum, palladium, rhodium, ruthenium, iridium and / or osmium. These non-magnetic residues are then packaged in big-bags or in bulk to be treated either by hydrometallurgy or by pyrometallurgy.
  • the hydrometallurgy may comprise a sulfuric acid etching step in an oxidizing medium, followed by an electrowining for recovering the copper, the etching residue being reduced in a rotating furnace containing lead in order to solubilize the metals.
  • Lead and tin can be refined by Betts type electrolysis, the sludge containing mainly precious metals.
  • the residues are recycled at the entrance to the copper furnaces, and the anodic sludge resulting from the electro-refining of the copper anodes poured out of the furnace is treated.
  • step (5) it is carried out concomitantly with step (2), since it concerns the treatment of gases resulting from pyrolysis.
  • the pyrolysis gases contain combustion products from the burners, water vapor and gases from the decomposition of epoxy resins and other carbon chain materials.
  • step (5) may advantageously be replaced by a step of condensation of the gaseous phase for the recovery of the products of the decomposition of the carbon chains (phenol, bisphenol, bromophenol and other components).
  • the method described above is used to process used electronic cards.
  • the ferrous metal fraction is reintroduced after the second magnetic separation.
  • the table below gives an estimate of the revolution of the chemical composition of the products during the various stages of the process.

Abstract

The invention relates to a method for treating materials containing a mixture of plastic materials and metal materials, said method including: - crushing the material to be treated; pyrolysis of the crushed material; a first magnetic separation performed on the pyrolysed material providing, on the one hand, a ferrous metal fraction and, on the other hand, non-ferrous residue; - a second magnetic separation performed on the non-ferrous residue providing, on the one hand, a non-ferrous metal fraction and, on the other hand, non-magnetic residue. The invention also relates to a facility for implementing said method.

Description

PROCEDE DE RECUPERATION DES METAUX CONTENUS DANS LES DECHETS ELECTRONIQUES A MATIERES PLASTIQUES PROCESS FOR RECOVERING METALS CONTAINED IN ELECTRONIC WASTE MATERIALS WITH PLASTIC MATERIALS
DOMAINE DE L'INVENTIONFIELD OF THE INVENTION
La présente invention concerne un procédé de récupération des métaux contenus dans les déchets électroniques, notamment les cartes électroniques usagées, ainsi qu'une installation adaptée à la mise en œuvre de ce procédé.The present invention relates to a method for recovering metals contained in electronic waste, in particular used electronic cards, and an installation adapted to the implementation of this method.
ARRIERE-PLAN TECHNIQUETECHNICAL BACKGROUND
L'accroissement de l'utilisation des calculatrices, des téléphones portables, des appareillages électroniques et autres appareils de haute technicité à courte durée de vie engendre une quantité croissante de déchets contenant typiquement des métaux ferreux, du cuivre, de l'aluminium, du zinc, des métaux rares et précieux... Cette situation pose le problème de la récupération et du traitement des métaux contenus dans ces déchets. Ainsi, de tels déchets constituent un véritable gisement de métaux.The increased use of calculators, mobile phones, electronic equipment and other short-lived high-tech devices is resulting in an increasing amount of waste typically containing ferrous metals, copper, aluminum, zinc , rare and precious metals ... This situation poses the problem of the recovery and treatment of the metals contained in this waste. Thus, such waste is a real deposit of metals.
Une technique connue de récupération des métaux consiste à charger les déchets (préalablement broyés à environ 4 cm) dans des fours primaires ou fours à cuivre. Cette technique engendre de fortes émissions de poussières, de dioxyde de soufre et de gaz contenant des halogènes (chlore et brome). Les gaz émis exigent donc un traitement ultérieur complexe. Un autre problème rencontré avec cette technique est que les déchets électroniques dégagent beaucoup de chaleur lors de la combustion du plastique qu'elles contiennent. En d'autres termes le pouvoir calorifique élevé des déchets électroniques est un obstacle à cette technique. La teneur en aluminium souvent élevée dans les déchets traités constitue encore un autre problème, puisque la présence d'aluminium dans les scories ou laitiers augmente leur température de fusion de façon telle que leur traitement devient très difficile. En raison de ces divers inconvénients, la capacité des fours primaires pour traiter les déchets électroniques est limitée.One known metal recovery technique is to load the waste (previously ground about 4 cm) into primary furnaces or copper furnaces. This technique generates high emissions of dust, sulfur dioxide and gases containing halogens (chlorine and bromine). The gases emitted therefore require complex subsequent processing. Another problem with this technique is that electronic waste gives off a lot of heat during the combustion of the plastic they contain. In other words, the high calorific value of electronic waste is an obstacle to this technique. The aluminum content often high in treated waste is another problem, since the presence of aluminum in the slag or dairy increases their melting temperature so that their treatment becomes very difficult. Because of these various disadvantages, the capacity of primary furnaces for processing electronic waste is limited.
D'autres techniques de récupération utilisent des procédés de broyage fin, suivi d'une séparation magnétique et électrostatique permettant d'enrichir et de trier des phases riches et pauvres en métaux. Par exemple, le document WO 2007/099204 présente une méthode comprenant le broyage des déchets en particules de 2-4 mm, la mise en charge électrostatique des matériaux par frottement contre un tambour, suivie d'un bombardement d'électrons, et enfin le tri des matériaux au moyen d'un champ électrique. Toutefois, les techniques de ce type sont onéreuses (en particulier en raison du broyage fin qui est nécessaire), n'assurent qu'un tri imparfait et aboutissent donc à un mauvais rendement de récupération des métaux précieux.Other recovery techniques use fine grinding processes, followed by magnetic and electrostatic separation to enrich and sort rich, metal-poor phases. For example, the document WO 2007/099204 presents a method comprising the grinding of the waste into particles of 2-4 mm, the electrostatic loading of the materials by friction against a drum, followed by electron bombardment, and finally the sorting of materials by means of an electric field. However, techniques of this type are expensive (especially because of the fine grinding that is necessary), provide only imperfect sorting and thus result in a poor recovery performance of precious metals.
Selon une autre approche, le document EP 1712301 décrit un procédé de traitement des déchets électroniques dans lequel les fragments de fil métalliques sont récupérés parmi les déchets au moyen d'un barillet muni d'une bande textile à laquelle les fragments de fil adhèrent.According to another approach, the document EP 1712301 describes a method of processing electronic waste in which the metal wire fragments are recovered from the waste by means of a barrel provided with a textile band to which the wire fragments adhere.
Des tentatives ont également été menées afin de récupérer les métaux par pyrolyse en lit fluidisé. Toutefois, cette technique a pour inconvénient de mélanger les métaux avec un additif (support de fluidisation) tel que du sable, du quartz..., ce qui complique la récupération. En effet, le tamisage qui est effectué en aval de la pyrolyse ne permet pas de séparer efficacement l'additif de certaines poussières métalliques. De plus un tel procédé consomme plus d'énergie, une partie des métaux s'oxydent et des métaux sont entraînés dans la phase gazeuse.Attempts have also been made to recover metals by pyrolysis in a fluidized bed. However, this technique has the disadvantage of mixing the metals with an additive (fluidization support) such as sand, quartz ..., which complicates the recovery. In fact, sieving which is carried out downstream of the pyrolysis does not make it possible to effectively separate the additive from certain metallic dusts. In addition, such a process consumes more energy, some of the metals oxidize and metals are entrained in the gas phase.
Il existe donc un réel besoin de mettre au point un procédé de récupération des métaux contenus dans les déchets électroniques, qui permette de surmonter les désavantages susmentionnés. En particulier, on souhaite mettre au point un procédé simple, consommant relativement peu d'énergie, ne nécessitant pas un traitement lourd des gaz émis, et permettant d'obtenir un bon rendement en métaux recyclés.There is therefore a real need to develop a process for recovering the metals contained in electronic waste, which overcomes the aforementioned disadvantages. In particular, it is desired to develop a simple process, consuming relatively little energy, not requiring a heavy treatment of the gases emitted, and to obtain a good yield of recycled metals.
RESUME DE L'INVENTIONSUMMARY OF THE INVENTION
L'invention concerne en premier lieu un procédé de traitement de matériaux contenant un mélange de matières plastiques et de matières métalliques, ledit procédé comprenant :The invention firstly relates to a method for treating materials containing a mixture of plastics and metal materials, said method comprising:
- le broyage des matériaux à traiter ;- the grinding of the materials to be treated;
- la pyrolyse des matériaux broyés ;pyrolysis of crushed materials;
- une première séparation magnétique effectuée sur les matériaux pyrolyses, fournissant d'une part une fraction métallique ferreuse et d'autre part des résidus non-ferreux ;a first magnetic separation carried out on the pyrolyzed materials, providing on the one hand a ferrous metal fraction and on the other hand non-ferrous residues;
- une deuxième séparation magnétique effectuée sur les résidus non-ferreux, fournissant d'une part une fraction métallique non-ferreuse et d'autre part des résidus non-magnétiques.a second magnetic separation carried out on the non-ferrous residues, providing on the one hand a non-ferrous metal fraction and on the other hand non-magnetic residues.
Selon un mode de réalisation, les matériaux sont des déchets électroniques, de préférence des cartes électroniques usagées.According to one embodiment, the materials are electronic waste, preferably used electronic cards.
Selon un mode de réalisation, le broyage est effectué jusqu'à un passant de tamis Dmax inférieur ou égal à 50 mm, de préférence compris entre 20 et 30 mm.According to one embodiment, the grinding is performed up to a sieve pass Dmax less than or equal to 50 mm, preferably between 20 and 30 mm.
Selon un mode de réalisation, la pyrolyse est effectuée à une température comprise entre 300 et 6000C et / ou avec un facteur d'air compris entre 0,7 et 0,98. Selon un mode de réalisation, la première séparation magnétique est effectuée au moyen d'un aimant ou électroaimant.According to one embodiment, the pyrolysis is carried out at a temperature of between 300 and 600 ° C. and / or with an air factor of between 0.7 and 0.98. According to one embodiment, the first magnetic separation is performed by means of a magnet or electromagnet.
Selon un mode de réalisation, la deuxième séparation magnétique est effectuée au moyen d'un séparateur à courants de Foucault.According to one embodiment, the second magnetic separation is performed by means of an eddy current separator.
Selon un mode de réalisation, le procédé comprend également une étape de combustion des gaz issus de la pyrolyse, éventuellement suivie d'une étape de neutralisation des gaz avec du bicarbonate de sodium.According to one embodiment, the method also comprises a step of combustion of the gases resulting from the pyrolysis, possibly followed by a step of neutralization of the gases with sodium bicarbonate.
Selon un mode de réalisation, la fraction métallique ferreuse comprend du fer et / ou des dérivés de fer, et éventuellement de l'or.According to one embodiment, the ferrous metal fraction comprises iron and / or iron derivatives, and possibly gold.
Selon un mode de réalisation, la fraction métallique non-ferreuse comprend de l'aluminium et / ou du zinc.According to one embodiment, the non-ferrous metal fraction comprises aluminum and / or zinc.
Selon un mode de réalisation, les résidus non-magnétiques comprennent du cuivre, du plomb, de l'étain, des fibres de verre, du carbone et / ou des métaux précieux, notamment de l'or, de l'argent, du platine, du palladium, du rhodium, du ruthénium, de l'iridium et / ou de l'osmium.According to one embodiment, the non-magnetic residues comprise copper, lead, tin, glass fibers, carbon and / or precious metals, in particular gold, silver, platinum , palladium, rhodium, ruthenium, iridium and / or osmium.
Selon un mode de réalisation, la fraction métallique ferreuse est combinée aux résidus non-magnétiques après la deuxième séparation magnétique.According to one embodiment, the ferrous metal fraction is combined with the non-magnetic residues after the second magnetic separation.
Selon un mode de réalisation, le procédé comprend une étape ultérieure de traitement des résidus non-magnétiques permettant de récupérer le cuivre contenu dans les résidus non-magnétiques et / ou de récupérer des métaux précieux contenus dans les résidus non-magnétiques, en particulier choisis parmi l'or, l'argent, le plomb, l'étain le platine, le palladium, le rhodium, le ruthénium, l'iridium et / ou l'osmium.According to one embodiment, the method comprises a subsequent step of treatment of the non-magnetic residues making it possible to recover the copper contained in the non-magnetic residues and / or to recover precious metals contained in the non-magnetic residues, in particular chosen among gold, silver, lead, tin, platinum, palladium, rhodium, ruthenium, iridium and / or osmium.
L'invention a également pour objet une installation de traitement de matériaux contenant un mélange de matières plastiques et de matières métall iques, comprenant successivement en ligne :The invention also relates to a material treatment plant containing a mixture of plastics and metallics, comprising successively online:
- des moyens de broyage ;grinding means;
- une installation de pyrolyse ;- a pyrolysis plant;
- un séparateur magnétique primaire ; eta primary magnetic separator; and
- un séparateur magnétique secondaire.a secondary magnetic separator.
Selon un mode de réalisation, les moyens de broyage sont adaptés pour effectuer un broyage jusqu'à un passant de tamis Dmax inférieur ou égal à 50 mm, de préférence compris entre 20 et 30 mm.According to one embodiment, the grinding means are adapted to carry out grinding up to a sieve pass Dmax less than or equal to 50 mm, preferably between 20 and 30 mm.
Selon un mode de réalisation, le séparateur magnétique primaire comprend un aimant ou électroaimant disposé au-dessus d'une bande de convoyage.According to one embodiment, the primary magnetic separator comprises a magnet or electromagnet disposed above a conveyor belt.
Selon un mode de réalisation, le séparateur magnétique secondaire comprend un séparateur à courants de Foucault. Selon un mode de réalisation, l'installation comprend également une conduite de collecte des gaz de pyrolyse alimentant une chambre de combustion, et éventuellement, en sortie de la chambre de combustion, une chambre de contact alimentée par un apport de charbon actif et un apport de bicarbonate de soude.According to one embodiment, the secondary magnetic separator comprises an eddy current separator. According to one embodiment, the installation also comprises a pyrolysis gas collection pipe supplying a combustion chamber, and optionally, at the outlet of the combustion chamber, a contact chamber fed by a supply of activated carbon and a supply of of baking soda.
La présente invention permet de surmonter les inconvénients de l'état de la technique. Elle fournit plus particulièrement un procédé simple et économe en énergie, permettant d'obtenir un bon rendement en métaux recyclés.The present invention overcomes the disadvantages of the state of the art. In particular, it provides a simple and energy-efficient process for obtaining a good yield of recycled metals.
Ceci est accompli grâce à la constatation surprenante que la pyrolyse directe de matériaux préalablement broyés de façon seulement grossière (un broyage fin étant inutile) permet d'obtenir directement un mélange des différents constituants sous forme individualisée : notamment les résidus carbonés d'une part et les différents métaux d'autre part.This is accomplished thanks to the surprising observation that the direct pyrolysis of previously crushed materials only in a coarse manner (fine grinding being unnecessary) makes it possible to directly obtain a mixture of the various constituents in individualized form: in particular the carbonaceous residues on the one hand and different metals on the other hand.
Selon certains modes de réalisation particuliers, l'invention présente également une ou plusieurs des caractéristiques avantageuses énumérées ci-dessous.According to some particular embodiments, the invention also has one or more of the advantageous features listed below.
Le procédé selon l'invention permet d'éliminer les résines époxy et les plastiques constituants des cartes électroniques ainsi que le chlore et une grande partie du brome tout en évitant une perte en métaux par oxydation ou distillation compte tenu de la basse température et des conditions non- oxydantes de l'opération. La matière est ainsi concentrée en métaux. Le procédé selon l'invention permet lors du refroidissement des gaz de combustion des gaz produits pendant la pyrolyse de récupérer dans de bonnes conditions l'énergie contenue dans ces gaz. La matière ainsi pyrolysée peut être traitée avantageusement dans les outils classiques de la métallurgie du cuivre en s'affranchissant de certaines limites technologiques de ces outils et plus précisément de la teneur en matières volatiles (chaînes carbonées) et des halogènes. Dans le cas du traitement des cartes électroniques, la décomposition des résines époxy lors de la pyrolyse a pour effet de l ibérer tous les composants solidaires du support : le cuivre, les composants électroniques, les composants métalliques... Cette désolidarisation du support permet une util isation très efficace d u tri mag nétiq ue (pl us efficace q ue l a désolidarisation que l'on opérerait par un broyage très fin). Le procédé selon l'invention permet de maximiser le rendement de récupération des métaux, c'est-à-dire de minimiser les pertes de métaux au cours du processus.The process according to the invention makes it possible to eliminate the epoxy resins and the plastics constituents of the electronic boards as well as chlorine and a large part of the bromine while avoiding a loss of metals by oxidation or distillation, taking into account the low temperature and the conditions non-oxidizing operation. The material is thus concentrated in metals. The method according to the invention makes it possible, during the cooling of the combustion gases, produced during pyrolysis, to recover the energy contained in these gases under good conditions. The material thus pyrolyzed can be treated advantageously in the conventional tools of copper metallurgy by overcoming certain technological limitations of these tools and more precisely the content of volatile matter (carbon chains) and halogens. In the case of electronic card processing, the decomposition of the epoxy resins during pyrolysis has the effect of liberating all the integral components of the support: copper, electronic components, metal components ... This separation of the support allows a very efficient use of mag- netic sorting (more effective than the separation that would be achieved by very fine grinding). The process according to the invention makes it possible to maximize the recovery efficiency of the metals, that is to say to minimize the losses of metals during the process.
Le procédé selon l'invention permet de séparer l'aluminium des autres métaux en cours de processus, de sorte à faciliter le traitement aval des métaux récupérés. Dans le cas des procédés pyro-métallurgiques, l'aluminium présente en effet un comportement néfaste à la fluidité des scories. Dans le cas des procédés hydro-métallurgiques, l'aluminium du fait de sa réactivité chimique entraîne une surconsommation de réactifs chimiques. Le traitement des gaz issus de la pyrolyse (comprenant une postcombustion) permet de rendre le procédé propre sans nécessiter de manipulation lourde d'halogènes, de composés soufrés ou d'émissions de métaux lourds.The process according to the invention makes it possible to separate the aluminum from the other metals during the process, so as to facilitate the downstream processing of the metals recovered. In the case of pyrometallurgical processes, aluminum indeed has a behavior that is detrimental to the fluidity of the slag. In the case of hydro-metallurgical processes, aluminum because of its chemical reactivity leads to overconsumption of chemical reagents. The treatment of pyrolysis gases (including post-combustion) makes the process clean without requiring heavy handling of halogens, sulfur compounds or heavy metal emissions.
BREVE DESCRIPTION DES FIGURESBRIEF DESCRIPTION OF THE FIGURES
La figure 1 représente de manière schématique un exemple d'installation de traitement de déchets électroniques selon l'invention.FIG. 1 schematically represents an example of an electronic waste treatment installation according to the invention.
DESCRIPTION DE MODES DE REALISATION DE L'INVENTIONDESCRIPTION OF EMBODIMENTS OF THE INVENTION
L'invention est maintenant décrite plus en détail et de façon non limitative dans la description qui suit.The invention is now described in more detail and without limitation in the description which follows.
Installation de traitement de déchets électroniquesElectronic waste treatment facility
En faisant référence à la figure 1 , une installation de traitement de déchets électroniques selon l'invention comprend de manière schématique les éléments qui suivent.Referring to Figure 1, an electronic waste processing facility according to the invention schematically comprises the following elements.
En entrée de l'installation de traitement est prévue une ligne d'amenée de déchets électroniques en vrac 1. Cette ligne d'amenée de déchets électroniques 1 alimente des moyens de broyage et d'échantillonnage 2. Les moyens de broyage et d'échantillonnage peuvent notamment comprendre un broyeur principal permettant de réduire la taille des déchets à moins de 50 mm, un échantillonneur primaire permettant de prélever un échantillon primaire représentatif du flux total (par exemple 10 % du flux total), un second broyeur permettant de broyer l'échantillon primaire à une taille de 10 mm, un échantillonneur secondaire représentatif de l'échantillon primaire (par exemple 10 % du flux de l'échantillon primaire), éventuellement un troisième broyeur et un échantillonneur tertiaire.At the inlet of the treatment plant there is provided a feed line for bulk electronic waste 1. This electronic waste feed line 1 feeds grinding and sampling means 2. The grinding and sampling means may include a main crusher to reduce the size of waste to less than 50 mm, a primary sampler to collect a primary sample representative of the total flow (for example 10% of the total flow), a second crusher for grinding the primary sample at a size of 10 mm, a secondary sampler representative of the primary sample (for example 10% of the flow of the primary sample), possibly a third mill and a tertiary sampler.
Un exemple préféré de broyeur principal est un broyeur à couteaux équipé d'une grille de 25 mm. Ce type de broyeur a l'avantage de limiter la production de fines.A preferred example of a main mill is a knife mill equipped with a 25 mm grid. This type of mill has the advantage of limiting the production of fines.
En sortie des moyens de broyage et d'échantillonnage 2, une ligne d'amenée de déchets broyés 3 alimente en déchets broyés une installation de pyrolyse 4. Un silo tampon (non représenté) peut être prévu entre les moyens de broyage et d'échantillonnage 2 et l'installation de pyrolyse 4. L'installation de pyrolyse 4 peut notamment être du type four à vis, four réverbère, four tournant, four à lit fluidisé, four à étages...At the outlet of the grinding and sampling means 2, a crushed waste feed line 3 feeds a pyrolysis plant 4 with crushed waste. A buffer silo (not shown) can be provided between the grinding and sampling means. 2 and the pyrolysis plant 4. The pyrolysis plant 4 can in particular, be of the type of oven, reverberatory oven, rotary kiln, fluidized bed furnace, multi-storey oven ...
De préférence, l'installation de pyrolyse 4 est un four à étages, par exemple d'environ 100 m2, chauffé directement au gaz. La puissance de l'installation peut être typiquement d'environ 1000 kW.Preferably, the pyrolysis plant 4 is a multi-stage furnace, for example approximately 100 m 2 , heated directly with gas. The power of the installation can typically be about 1000 kW.
En sortie de l'installation de pyrolyse 4 sont prévues une ligne d'amenée de résidus pyrolyses 5 et une conduite de collecte des gaz de pyrolyse 15.At the outlet of the pyrolysis plant 4 there is provided a pyrolytic residue feed line 5 and a pyrolysis gas collection pipe 15.
La ligne d'amenée de résidus pyrolyses 5 alimente des moyens de refroidissement 6. Les moyens de refroidissement 6 peuvent notamment comprendre un échangeur de chaleur. Une vis jacketée d'environ 50 m2 de surface et refroidie à l'eau peut notamment être appropriée.The pyrolyzed residue feed line 5 feeds cooling means 6. The cooling means 6 may in particular comprise a heat exchanger. A jacketed screw of approximately 50 m 2 surface and cooled with water may in particular be appropriate.
En sortie des moyens de refroidissement 6, une ligne d'amenée de résidus refroidis 7 alimente un séparateur magnétique primaire 8. Le séparateur magnétique primaire 8 peut être un simple électroaimant disposé au-dessus d'une bande de convoyage.At the outlet of the cooling means 6, a cooled residue feeding line 7 feeds a primary magnetic separator 8. The primary magnetic separator 8 can be a simple electromagnet disposed above a conveyor belt.
Une ligne de récupération de fraction métallique ferreuse 9 et une ligne de récupération de résidus non-ferreux 10 sont connectées en sortie du séparateur magnétique primaire 8.A ferrous metal fraction recovery line 9 and a non-ferrous residue recovery line 10 are connected at the output of the primary magnetic separator 8.
La ligne de récupération de résidus non-ferreux 10 alimente à son tour un séparateur magnétique secondaire 1 1 , appareil spécialement conçu pour cette fonction. Le séparateur magnétique secondaire 11 peut par exemple utiliser des courants de Foucault.The non-ferrous waste recovery line 10 in turn feeds a secondary magnetic separator 11, a device specially designed for this function. The secondary magnetic separator 11 may for example use eddy currents.
Une ligne de récupération de fraction métallique non-ferreuse 12 et une ligne de récupération de résidus non magnétiques 13 sont connectées en sortie du séparateur magnétique secondaire 11. La ligne de récupération de résidus non magnétiques 13 alimente à son tour des moyens de conditionnement 14.A non-ferrous metal fraction recovery line 12 and a non-magnetic residue recovery line 13 are connected at the output of the secondary magnetic separator 11. The non-magnetic residue recovery line 13 supplies conditioning means 14 in turn.
Selon un mode de réalisation particulier, la conduite de collecte des gaz de pyrolyse 15 alimente une chambre de combustion 17, qui est également alimentée par une conduite d'arrivée d'air 16. La chambre de combustion 17 peut être du type chambre cylindrique métallique protégée par une ou plusieurs couches de briques.According to a particular embodiment, the pyrolysis gas collection pipe 15 feeds a combustion chamber 17, which is also fed by an air inlet pipe 16. The combustion chamber 17 may be of the metallic cylindrical chamber type protected by one or more layers of bricks.
En sortie de la chambre de combustion 17, une conduite de collecte des produits de combustion 18 alimente des moyens de refroidissement 19. Les moyens de refroidissement 19 peuvent par exemple consister en une tour de refroidissement 19, alimentée par une injection d'eau pulvérisée 20, ou un échangeur refroidisseur de fumées (air-fumées ou eau-fumées).At the outlet of the combustion chamber 17, a combustion products collection pipe 18 feeds cooling means 19. The cooling means 19 may for example consist of a cooling tower 19 supplied with a water spray injection. , or a heat exchanger for flue gas (air-fumes or water-fumes).
Une conduite de collecte des produits de combustion refroidis 26 est connectée en sortie des moyens de refroidissement 19 et alimente une chambre de contact 29. Un apport de charbon actif 27 et un apport de bicarbonate de soude 28 sont également prévus en entrée de la chambre de contact 29. La chambre de contact 29 peut être du type cylindrique ayant un volume suffisant permettant d'avoir un temps de séjour des produits de combustion d'environ deux secondes.A collection duct for the cooled combustion products 26 is connected at the outlet of the cooling means 19 and supplies a contact chamber 29. A supply of activated carbon 27 and a supply of sodium bicarbonate 28 are also provided at the inlet of the contact chamber 29. The contact chamber 29 may be of the cylindrical type having a sufficient volume to have a residence time of the combustion products of about two seconds.
En sortie de la chambre de contact 29, une conduite de collecte de produits traités 30 alimente un filtre 31 en sortie duquel sont prévues une ligne de récupération de gaz épurés 33 et une ligne de récupération d'halogènes 32. Le filtre 31 peut être du type filtre à manches ou électro-filtre.At the outlet of the contact chamber 29, a product collection line 30 feeds a filter 31 at the output of which are provided a purified gas recovery line 33 and a halogen recovery line 32. The filter 31 may be type bag filter or electro-filter.
Selon une possibilité optionnelle, on peut prévoir un système de refroidissement prél iminaire en amont des moyens de refroidissement 19. Ce système de refroidissement préliminaire comprend une conduite de prélèvement 21 en sortie de la chambre de combustion 17, qui alimente un échangeur 24, puis rejoint la conduite de collecte des produits de combustion 18. L'échangeur 24 est également alimenté par une amenée de fluide caloporteur 23. La sortie 25 du fluide caloporteur assure la récupération de l'énergie.According to an optional possibility, it is possible to provide a preliminary cooling system upstream of the cooling means 19. This preliminary cooling system comprises a sampling pipe 21 at the outlet of the combustion chamber 17, which feeds a heat exchanger 24 and then rejoins the collection pipe of the combustion products 18. The heat exchanger 24 is also supplied by a supply of coolant 23. The outlet 25 of the coolant ensures the recovery of energy.
Procédé de traitement de déchets électroniquesElectronic waste treatment method
On décrit ci-dessous un exemple de procédé de traitement de déchets électroniques permettant une valorisation des métaux qu'ils contiennent.An example of a method of processing electronic waste for recovering the metals they contain is described below.
Par « déchets électroniques » on entend les matériaux usagés comprenant des composants électroniques. Les déchets électroniques peuvent comprendre des composants électroniques individuels, des téléphones portables et tous autres appareils de petite taille contenant des cartes électroniques. De manière préférée, les déchets électroniques comprennent ou consistent en des cartes électroniques, c'est-à-dire des plaquettes constituées de circuits imprimés sur lesquels sont soudés des composants électroniques. La suite du procédé est donc décrite en relation avec le recyclage des cartes électroniques.By "electronic waste" is meant used materials comprising electronic components. Electronic waste may include individual electronic components, mobile phones and any other small device containing electronic cards. Preferably, the electronic scrap comprises or consists of electronic boards, that is to say platelets consisting of printed circuits on which are welded electronic components. The following process is described in connection with the recycling of electronic cards.
Le procédé trouve toutefois également à s'appliquer dans le cas d'autres types de matériaux de départ, à savoir de manière générale les matériaux (de préférence matériaux usagés ou déchets) comprenant une fraction métallique (notamment une fraction métallique contenant des métaux précieux) et une fraction plastique. La fraction plastique peut comprendre notamment des résines époxys, du polyéthylène ou du polychlorure de vinyle. Et la fraction métallique peut comprendre notamment des métaux ferreux, du cuivre, du plomb, de l'aluminium, du zinc, des métaux précieux (or, argent, platine, palladium, rhodium, ruthénium, iridium, osmium). Par exemple, le procédé peut s'appliquer à des résidus de broyage automobile.However, the method is also applicable in the case of other types of starting materials, namely generally materials (preferably used materials or waste) comprising a metal fraction (including a metal fraction containing precious metals) and a plastic fraction. The plastic fraction can comprise in particular epoxy resins, polyethylene or polyvinyl chloride. And the metal fraction can include ferrous metals, copper, lead, aluminum, zinc, precious metals (gold, silver, platinum, palladium, rhodium, ruthenium, iridium, osmium). For example, the process can be applied to automotive grinding residues.
Le procédé décrit ici comprend les 5 étapes principales suivantes :The method described here comprises the following 5 main steps:
(1 ) broyage ; (2) pyrolyse ;(1) grinding; (2) pyrolysis;
(3) refroidissement ;(3) cooling;
(4) tris magnétiques ; et(4) magnetic sorts; and
(5) traitement des gaz.(5) gas treatment.
Cet exemple correspond à l'utilisation de l'installation de traitement décrite ci- dessus en relation avec la figure 1.This example corresponds to the use of the processing installation described above in connection with FIG.
La capacité de traitement est de l'ordre de 3 tonnes par heure.The treatment capacity is of the order of 3 tons per hour.
A l'étape (1 ), les cartes électroniques sont broyées au niveau des moyens de broyage 2. Le broyage s'effectue de préférence jusqu'à une taille Dmax de 25 mm (Dmax étant défini comme le passant de tamis). Les cartes broyées sont ensuite stockées dans un silo tampon.In step (1), the electronic cards are crushed at the level of the grinding means 2. The grinding is preferably carried out to a size Dmax of 25 mm (Dmax being defined as the sieve pass). The crushed cards are then stored in a buffer silo.
Le silo tampon alimente à environ 3 tonnes par heure l'installation de pyrolyse 4, dans laquelle on procède à la pyrolyse de l'étape (2). Pour cette étape (2), on chauffe les cartes broyées dans le four jusqu'à une température comprise entre 300 et 4500C, de préférence d'environ 4000C, dans un réacteur adapté, et ce essentiellement en l'absence d'oxygène (en milieu réducteur ou neutre). Plus précisément, les brûleurs sont réglés avec un défaut d'air et le facteur d'air (rapport entre l'air de combustion et l'air théorique de combustion neutre) est compris entre 0,7 et 0,9. La durée de la pyrolyse est ajustée afin d'obtenir une décomposition complète des chaînes carbonées composant la fraction plastique (notamment les chaînes des résines époxys). Par exemple, la durée peut être comprise entre 10 et 30 minutes. Un ajout de vapeur d'environ 1 tonne/heure au niveau des étages du four permet de maîtriser la température de ceux-ci.The buffer silo supplies the pyrolysis plant 4 at about 3 tons per hour, in which pyrolysis of step (2) is carried out. For this step (2), the ground boards are heated in the oven to a temperature of between 300 and 450 ° C., preferably about 400 ° C., in a suitable reactor, essentially in the absence of oxygen (in reducing or neutral medium). More precisely, the burners are regulated with a defect of air and the air factor (ratio between the combustion air and the theoretical neutral combustion air) is between 0.7 and 0.9. The duration of the pyrolysis is adjusted in order to obtain a complete decomposition of the carbon chains composing the plastic fraction (in particular the chains of the epoxy resins). For example, the duration can be between 10 and 30 minutes. A steam addition of about 1 ton / hour at the levels of the furnace can control the temperature thereof.
Au cours de l'étape (3), les résidus pyrolyses passent par les moyens de refroidissement 6. Cette étape permet de réduire la température des résidus pyrolyses jusqu'à une température comprise entre 60 et 100°C.During step (3), the pyrolysis residues pass through the cooling means 6. This step makes it possible to reduce the temperature of the pyrolyzed residues to a temperature of between 60 and 100 ° C.
Puis, l'étape (4) comprend la séparation proprement dite des métaux. Cette étape permet d'enrichir le résidu solide en métaux précieux et de diminuer la concentration des éléments nuisibles au traitement ultérieur du résidu pyrolyse (notamment l'aluminium).Then, step (4) comprises the actual separation of the metals. This step makes it possible to enrich the solid residue with precious metals and to reduce the concentration of harmful elements in the subsequent treatment of the pyrolysis residue (in particular aluminum).
Dans un premier temps, les résidus refroidis passent par le séparateur magnétique primaire 8, typiquement un simple électroaimant disposé au-dessus d'un convoyeur à bande. Ainsi, on extrait la fraction métallique ferreuse des résidus. Cette fraction métallique ferreuse comprend principalement le fer et les dérivés du fer, mais éventuellement, selon l'origine des cartes électroniques, la fraction métallique ferreuse peut aussi comprendre (être mêlée à) de l'or. C'est le cas notamment lorsque les cartes électroniques sont flashées à l'or. De préférence, la fraction métallique ferreuse ne comprend pas plus de 1 % d'aluminium.Firstly, the cooled residues pass through the primary magnetic separator 8, typically a single electromagnet disposed above a belt conveyor. Thus, the ferrous metal fraction is extracted from the residues. This ferrous metal fraction mainly comprises iron and iron derivatives, but possibly, depending on the origin of the electronic cards, the ferrous metal fraction may also include (be mixed with) gold. This is particularly the case when the electronic cards are flashed with gold. Preferably, the ferrous metal moiety does not comprise more than 1% aluminum.
Dans un deuxième temps, les résidus débarrassés de la fraction métallique ferreuse subissent une extraction magnétique des non-ferreux au niveau du séparateur magnétique secondaire 11 , typiquement en utilisant des courants de Foucault. Ainsi, on extrait une fraction métallique non-ferreuse, qui comprend notamment de l'aluminium et du zinc. L'aluminium ainsi récupéré peut être vendu pour être recyclé. D'un autre côté, le reste des résidus (résidus non magnétiques) est récupéré via la ligne de récupération de résidus non magnétiques 13. De préférence, les résidus non magnétiques ne comprennent pas plus de 2 % d'aluminium.In a second step, the residues freed from the ferrous metal fraction undergo magnetic extraction of the non-ferrous metals at the secondary magnetic separator 11, typically using eddy currents. Thus, a non-ferrous metal fraction is extracted, which notably comprises aluminum and zinc. The recovered aluminum can be sold for recycling. On the other hand, the rest of the residues (non-magnetic residues) are recovered via the non-magnetic residue recovery line 13. Preferably, the non-magnetic residues do not comprise more than 2% of aluminum.
Afin de pouvoir effectuer l'extraction magnétique des non-ferreux par courants de Foucault, il importe que la fraction métallique non-ferreuse (et notamment l'aluminium) soit sous forme essentiellement non-oxydée. Par conséquent, le procédé est mis en œuvre de telle sorte que les métaux composant la fraction métallique non-ferreuse, et en premier lieu l'aluminium, ne sont pas oxydés avant l'étape d'extraction magnétique des non-ferreux. Typiquement, en cas de chauffage par flamme directe, le réglage de la flamme est effectué avec un déficit d'oxygène (par exemple 90 % de la stœchiométrie) ; en cas de chauffage indirect, l'atmosphère doit être réductrice. Par ailleurs, on préfère travailler en dessous du point de fusion de l'aluminium, afin d'éviter que des traces d'oxygène n'oxydent le métal fondu (plus facile à oxyder que le métal solide).In order to be able to carry out the magnetic extraction of nonferrous by eddy currents, it is important for the non-ferrous metal fraction (and in particular aluminum) to be in substantially non-oxidized form. Therefore, the process is carried out so that the metals composing the non-ferrous metal fraction, and primarily aluminum, are not oxidized before the non-ferrous magnetic extraction step. Typically, in case of heating by direct flame, the adjustment of the flame is carried out with a deficit of oxygen (for example 90% of the stoichiometry); in case of indirect heating, the atmosphere must be reducing. Furthermore, it is preferred to work below the melting point of aluminum, in order to prevent traces of oxygen from oxidizing the molten metal (which is easier to oxidize than the solid metal).
Selon la teneur en métaux précieux de la fraction métallique ferreuse, il est possible soit de valoriser séparément la fraction métallique ferreuse soit de la mélanger à nouveau avec la fraction des résidus non magnétiques après la deuxième séparation magnétique (au niveau de la ligne de récupération de résidus non magnétiques 13).Depending on the precious metal content of the ferrous metal fraction, it is possible either to separately recover the ferrous metal fraction or to mix it again with the fraction of the non-magnetic residues after the second magnetic separation (at the level of the recovery line of non-magnetic residues 13).
La valorisation de la fraction métallique ferreuse peut comprendre une récupération des métaux précieux qu'elle contient par exemple selon les procédés suivants : recyclage de la partie magnétique riche en métaux précieux à l'entrée des fours à cuivre, et traitement des boues anodiques issues de l'électro-raffinage des anodes en cuivre coulées en sortie de four ; lavage au plomb de la partie magnétique pour solubiliser dans le plomb les métaux précieux, et traitement du plomb selon toute méthode conventionnelle pour récupérer ces métaux précieux (telle que zingage, distillation et coupellation, ou traitement sur un électroraffinage de type Betts).The valorization of the ferrous metal fraction may include a recovery of the precious metals it contains for example according to the following processes: recycling of the magnetic part rich in precious metals at the entrance of copper furnaces, and treatment of anode sludges from electro-refining copper anodes poured out of the oven; lead wash of the magnetic part to solubilize precious metals in lead, and treatment of lead according to any conventional method for recovering these precious metals (such as zinc coating, distillation and cupellation, or treatment on a Betts type of electrorefining).
Les résidus non magnétiques comprennent notamment du carbone, des fibres de verre, du cuivre, du plomb, de l'étain et généralement des métaux précieux. Les métaux précieux en question peuvent comprendre de l'or, de l'argent, du platine, du palladium, du rhodium, du ruthénium, de l'iridium et / ou de l'osmium. Ces résidus non magnétiques sont ensuite conditionnés en big-bags ou en vrac pour être traités soit par hydrométallurgie soit par pyrométallurgie.Non-magnetic residues include carbon, glass fibers, copper, lead, tin and generally precious metals. The precious metals in question may include gold, silver, platinum, palladium, rhodium, ruthenium, iridium and / or osmium. These non-magnetic residues are then packaged in big-bags or in bulk to be treated either by hydrometallurgy or by pyrometallurgy.
L'hydrométallurgie peut comprendre une étape d'attaque par de l'acide sulfurique en milieu oxydant, suivie d'un électrowining permettant de récupérer le cuivre, les résidus d'attaque étant réduits dans un four tournant contenant du plomb afin de solubiliser les métaux précieux, l'étain et le plomb. Le plomb et l'étain peuvent être raffinés par une électrolyse de type Betts, les boues contenant essentiellement les métaux précieux.The hydrometallurgy may comprise a sulfuric acid etching step in an oxidizing medium, followed by an electrowining for recovering the copper, the etching residue being reduced in a rotating furnace containing lead in order to solubilize the metals. precious, tin and lead. Lead and tin can be refined by Betts type electrolysis, the sludge containing mainly precious metals.
Dans le cadre de la pyrométallurgie, les résidus sont recyclés à l'entrée des fours à cuivre, puis on traite les boues anodiques issues de l'électro-raffinage des anodes en cuivre coulées à la sortie du four.In the framework of pyrometallurgy, the residues are recycled at the entrance to the copper furnaces, and the anodic sludge resulting from the electro-refining of the copper anodes poured out of the furnace is treated.
Quant à l'étape (5), elle est effectuée concomitamment à l'étape (2), puisqu'elle concerne le traitement des gaz issus de la pyrolyse.As for step (5), it is carried out concomitantly with step (2), since it concerns the treatment of gases resulting from pyrolysis.
Les gaz issus de la pyrolyse contiennent des produits de combustion des brûleurs, de la vapeur d'eau ainsi que les gaz issus de la décomposition des résines époxy et autres matières à chaînes carbonées.The pyrolysis gases contain combustion products from the burners, water vapor and gases from the decomposition of epoxy resins and other carbon chain materials.
Ces gaz sont brûlés dans la chambre de combustion 17 à une température suffisante pour permettre la destruction des dioxines. Une température comprise entre environ 850 et environ 11000C peut être appropriée. De l'acide chlorhydrique et de l'acide bromhydrique sont ainsi produits.These gases are burned in the combustion chamber 17 at a temperature sufficient to allow the destruction of dioxins. A temperature between about 850 and about 1100 0 C may be appropriate. Hydrochloric acid and hydrobromic acid are thus produced.
Après refroidissement des gaz à une température comprise entre environ 180 et environ 2000C (au niveau des moyens de refroidissement 19), on procède à une injection de charbon actif (par exemple environ 50 mg/m3) et de bicarbonate de sodium (par exemple environ 20 kg/h) afin de fixer le reste de dioxines, et de faire réagir HCI et HBr avec le bicarbonate du sodium pour former du bromure et du chlorure de sodium. Les réactions ont lieu dans la chambre de contact 29, avec un temps de contact d'environ 2 secondes.After cooling the gases to a temperature of between about 180 and about 200 ° C. (at the level of the cooling means 19), an injection of activated charcoal (for example about 50 mg / m 3 ) and sodium bicarbonate ( for example about 20 kg / h) to fix the remainder of dioxins, and to react HCl and HBr with sodium bicarbonate to form bromide and sodium chloride. The reactions take place in the contact chamber 29, with a contact time of about 2 seconds.
Après filtration, on récupère essentiellement un mélange de bromure de sodium et de chlorure de sodium ; ce mélange peut être valorisé pour récupération du brome.After filtration, a mixture of sodium bromide and sodium chloride is essentially recovered; this mixture can be valorized for bromine recovery.
On peut également prévoir de récupérer l'énergie des produits de combustion (échange de chaleur au niveau de l'échangeur 24), cette énergie pouvant être recyclée à d'autres étapes du procédé.It is also possible to recover the energy of the combustion products (heat exchange at the exchanger 24), this energy can be recycled at other stages of the process.
Il faut noter que l'étape (5) peut avantageusement être remplacée par une étape de condensation de la phase gazeuse pour la valorisation des produits de la décomposition des chaînes carbonées (phénol, bisphénol, bromophénol et autres composants). EXEMPLEIt should be noted that step (5) may advantageously be replaced by a step of condensation of the gaseous phase for the recovery of the products of the decomposition of the carbon chains (phenol, bisphenol, bromophenol and other components). EXAMPLE
Le présent exemple illustre l'invention sans la limiter.This example illustrates the invention without limiting it.
On met en œuvre le procédé décrit ci-dessus pour traiter des cartes électroniques usagées. On réintroduit la fraction métallique ferreuse après la deuxième séparation magnétique. Le tableau ci-dessous donne une estimation de révolution de la composition chimique des produits au cours des différentes étapes du procédé.The method described above is used to process used electronic cards. The ferrous metal fraction is reintroduced after the second magnetic separation. The table below gives an estimate of the revolution of the chemical composition of the products during the various stages of the process.

Claims

REVENDICATIONS
1. Procédé de traitement de matériaux contenant un mélange de matières plastiques et de matières métalliques, ledit procédé comprenant :A method of treating materials containing a mixture of plastics and metallic materials, said method comprising:
- le broyage des matériaux à traiter ;- the grinding of the materials to be treated;
- la pyrolyse des matériaux broyés ;pyrolysis of crushed materials;
- une première séparation magnétique effectuée sur les matériaux pyrolyses, fournissant d'une part une fraction métallique ferreuse et d'autre part des résidus non-ferreux ;a first magnetic separation carried out on the pyrolyzed materials, providing on the one hand a ferrous metal fraction and on the other hand non-ferrous residues;
- une deuxième séparation magnétique effectuée sur les résidus non-ferreux, fournissant d'une part une fraction métallique non-ferreuse et d'autre part des résidus non-magnétiques comprenant des métaux précieux.a second magnetic separation carried out on the non-ferrous residues, providing on the one hand a non-ferrous metal fraction and on the other hand non-magnetic residues comprising precious metals.
2. Procédé selon la revendication 1 , dans lequel les matériaux sont des déchets électroniques, de préférence des cartes électroniques usagées.2. The method of claim 1, wherein the materials are electronic waste, preferably used electronic cards.
3. Procédé selon la revendication 1 ou 2, dans lequel le broyage est effectué jusqu'à un passant de tamis Dmax inférieur ou égal à 50 mm, de préférence compris entre 20 et 30 mm.3. Method according to claim 1 or 2, wherein the grinding is performed to a sieve pass Dmax less than or equal to 50 mm, preferably between 20 and 30 mm.
4. Procédé selon l'une des revendications 1 à 3, dans lequel la pyrolyse est effectuée à une température comprise entre 300 et 6000C et / ou avec un facteur d'air compris entre 0,7 et 0,98.4. Method according to one of claims 1 to 3, wherein the pyrolysis is carried out at a temperature between 300 and 600 0 C and / or with an air factor of between 0.7 and 0.98.
5. Procédé selon l'une des revendications 1 à 4, dans lequel la première séparation magnétique est effectuée au moyen d'un aimant ou électroaimant.5. Method according to one of claims 1 to 4, wherein the first magnetic separation is performed by means of a magnet or electromagnet.
6. Procédé selon l'une des revendications 1 à 5, dans lequel la deuxième séparation magnétique est effectuée au moyen d'un séparateur à courants de Foucault.6. Method according to one of claims 1 to 5, wherein the second magnetic separation is performed by means of an eddy current separator.
7. Procédé selon l'une des revendications 1 à 6, comprenant également une étape de combustion des gaz issus de la pyrolyse, éventuellement suivie d'une étape de neutralisation des gaz avec du bicarbonate de sodium. 7. Method according to one of claims 1 to 6, also comprising a combustion step of the gases from the pyrolysis, optionally followed by a step of neutralization of the gas with sodium bicarbonate.
8. Procédé selon l'une des revendications 1 à 7, dans lequel les métaux précieux comprennent de l'or, de l'argent, du platine, du palladium, du rhodium, du ruthénium, de l'iridium et / ou de l'osmium.8. Process according to one of claims 1 to 7, in which the precious metals comprise gold, silver, platinum, palladium, rhodium, ruthenium, iridium and / or 'osmium.
9. Procédé selon l'une des revendications 1 à 8, dans lequel :9. Method according to one of claims 1 to 8, wherein:
- la fraction métallique ferreuse comprend du fer et / ou des dérivés de fer, et éventuellement de l'or ; et / outhe ferrous metal fraction comprises iron and / or iron derivatives, and possibly gold; and or
- la fraction métallique non-ferreuse comprend de l'aluminium et / ou du zinc.the non-ferrous metal fraction comprises aluminum and / or zinc.
10. Procédé selon l'une des revendications 1 à 9, dans lequel les résidus non- magnétiques comprennent du cuivre, du plomb, de l'étain, des fibres de verre, du carbone.10. Process according to one of claims 1 to 9, wherein the non-magnetic residues comprise copper, lead, tin, glass fibers, carbon.
11. Procédé selon l'une des revendications 1 à 10, dans lequel la fraction métallique ferreuse est combinée aux résidus non-magnétiques après la deuxième séparation magnétique.11. Method according to one of claims 1 to 10, wherein the ferrous metal fraction is combined with the non-magnetic residues after the second magnetic separation.
12. Procédé selon l'une des revendications 1 à 11 , comprenant une étape ultérieure de traitement des résidus non-magnétiques permettant de récupérer le cuivre contenu dans les résidus non-magnétiques et / ou de récupérer des métaux précieux contenus dans les résidus non-magnétiques, en particulier choisis parmi l'or, l'argent, le plomb, l'étain le platine, le palladium, le rhodium, le ruthénium, l'iridium et / ou l'osmium.12. Method according to one of claims 1 to 11, comprising a subsequent step of treatment of non-magnetic residues for recovering the copper contained in the non-magnetic residues and / or recovering precious metals contained in the non-magnetic residues. magnets, in particular chosen from gold, silver, lead, tin, platinum, palladium, rhodium, ruthenium, iridium and / or osmium.
13. Installation de traitement de matériaux contenant un mélange de matières plastiques et de matières métalliques, comprenant successivement en ligne : des moyens de broyage (2) ; une installation de pyrolyse (4) ; un séparateur magnétique primaire (8) ; et un séparateur magnétique secondaire (11 ).13. A material treatment plant containing a mixture of plastics and metallic materials, comprising successively in line: grinding means (2); a pyrolysis plant (4); a primary magnetic separator (8); and a secondary magnetic separator (11).
14. Installation selon la revendication 13, dans laquelle les moyens de broyage sont adaptés pour effectuer un broyage jusqu'à un passant de tamis Dmax inférieur ou égal à 50 mm, de préférence compris entre 20 et 30 mm. 14. Installation according to claim 13, wherein the grinding means are adapted to perform grinding up to a sieve pass Dmax less than or equal to 50 mm, preferably between 20 and 30 mm.
15. Installation selon la revendication 13 ou 14, dans laquelle le séparateur magnétique primaire (8) comprend un aimant ou électroaimant disposé au- dessus d'une bande de convoyage.15. Installation according to claim 13 or 14, wherein the primary magnetic separator (8) comprises a magnet or electromagnet disposed above a conveyor belt.
16. Installation selon l'une des revendications 13 à 15, dans laquelle le séparateur magnétique secondaire (11 ) comprend un séparateur à courants de Foucault.16. Installation according to one of claims 13 to 15, wherein the secondary magnetic separator (11) comprises an eddy current separator.
17. Installation selon l'une des revendications 13 à 16, comprenant également une conduite de collecte des gaz de pyrolyse (15) alimentant une chambre de combustion (17), et éventuellement, en sortie de la chambre de combustion (17), une chambre de contact (29) alimentée par un apport de charbon actif (27) et un apport de bicarbonate de soude (28). 17. Installation according to one of claims 13 to 16, also comprising a pyrolysis gas collection pipe (15) supplying a combustion chamber (17), and optionally, at the outlet of the combustion chamber (17), a contact chamber (29) fed by a supply of activated carbon (27) and a supply of sodium bicarbonate (28).
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MX2011005035A (en) 2011-08-17
PL2366038T3 (en) 2018-08-31
BRPI0916113B1 (en) 2018-11-27
PT2366038T (en) 2018-05-24
CN102216476A (en) 2011-10-12
FR2938457A1 (en) 2010-05-21
KR20110087312A (en) 2011-08-02
JP2012508825A (en) 2012-04-12
WO2010055489A1 (en) 2010-05-20
CA2743278A1 (en) 2010-05-20
CA2743278C (en) 2018-04-03
HRP20180734T1 (en) 2018-06-29
ES2669065T3 (en) 2018-05-23

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